DE3327299A1 - BLUE-SHAPED FILM ELEMENT - Google Patents

Description

The invention relates to new, layerable, high-long-chain branched, non-gelled, preferably end-blocked, non-linear Phenoxy resins with any structure or random structure without regularly recurring units, their average The distance between the branch points is essentially of the same order of magnitude as the average branch length. The invention also relates to vesicular ones Films and in particular compositions suitable for this purpose, which contain the above-mentioned non-linear, high-long-chain-branched, preferably contain end-blocked phenoxy resins as a carrier or matrix for a vesification agent.

Vesicular images are used in photographic Filming is formed by refraction of light from small bubbles or vesicles of gas that are present in the exposed areas of the film are formed and captured, followed by development. The films generally have a resinous shape Coating containing a photosensitive vesiculating agent. The cover is on deposited on a photographic film or substrate. The photosensitive vesification agent is generally used referred to as a sensitizer. The most widely used sensitizers are diazo compounds, which act after exposure the light or exposure generate nitrogen gas. The gas forms Although not bubbles immediately, it does so after the thermal development of the film, which causes the microdispersed gaseous material can grow together and form bubbles.

The resulting bubbles in the exposed area make the matrix against the penetration of light in such Areas impermeable.

Successful vesicular imaging regardless of the gas used to develop the vesicles in the matrix polymer, e.g., oxygen, isobutylene, carbon dioxide or Nitrogen, the basic physical requirement regarding

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the critical minimum bubble radius to the gas pressure that leads to it is available to do the work needed to remove the vesicle from the initial location of the vesicle or the To expand nucleation center. The gas pressure available from the imagewise photolysis of the gas progenitor and the dynamics of bubble formation depend on a complex interplay between the characteristics of the polymer matrix, i.e. the gas solubility in the matrix, the nucleation sites, the flow properties of the matrix and the gas barrier properties, away. The matrix or carrier in which the sensitizer or vesifying agent is dispersed and in which the bubbles are formed after exposure and development, is therefore one of the essential components which influence the behavior of a vesicle-forming film. It is generally believed that the bearers' own Shafts are dominant for the selection of the optimal matrix polymers for the vesicle-shaped image, since they are absent of good gas barrier properties none of the further requirements either alone or in combination is sufficient to provide a suitable vesicular imaging film.

For the past two decades there has been commercial interest in the benefits of dry development processes on vesicle-shaped Films have led to intense research in this area, which has led to the conclusion that the relatively few Polymer classes that have adequate gas barrier properties have been identified. Examples of this are saran, Poly (alpha-chloroacrylonitrile), polymethacrylonitrile and various Copolymers and terpolymers of the latter two monomers. Therefore, the search for new polymers with superior ' Blistering properties further.

The excellent barrier properties of certain linear, i.e. non-branched and non-crosslinked phenoxy resins against gases and moisture vapors are in the Literature well documented; See, e.g., New Linear Polymers by Lee et al., pp. 52 and 53 (1967). These resins are therefore

drew carriers for vesicular films. In fact, in U.S. Patent 3,622,333 discloses the suitability of such linear phenoxy resins as matrix resins for vesicular diazo imaging films written at a relatively slow speed. It can

However, it can be extremely difficult to find one in an economical manner To obtain sufficient 'degree of polymerisation of such linear resins, in this way to produce a highly viscous coating solution and in particular to obtain a coating solution having a viscosity high enough that the solution is coated by precision coating techniques.

There is also the use of branched novolak phenoxy resins known as matrix resins. US Pat. No. 4,330,524 discloses a photosensitive composition for vesicular imaging

.15 described which a branched novolak epoxy resin from a Contains bisglycidyl ether and a dihydric phenol. Gelation problems however, during polymerization can make the synthesis of such branched polymer structures very difficult and make them more expensive. Such branched polymer structures are best obtained by grafting techniques, but this procedure results in relatively poor control the polymer structure and the simultaneous homopolymer formation. There is therefore a need for the possibility a quick and - what is more important - reproducible control of the branch chain length and the molecular weight branched phenoxy resins to minimize microgelling and gelation during polymerization to exclude.

The object of the invention is therefore to provide a resin available that quickly, economically and reproducibly to a highly viscous state, if desired, polymerized without gelation which has excellent properties for use as a carrier for vesicular films.

The invention is also intended to provide new, non-linear or branched phenoxy resins which are large

Applicability as a matrix resin for vesicular films and in particular for bubble-shaped diazo imaging films with increased Can find photosensitivity.

The invention is also intended to provide a method for the simple production of a non-linear / i.e. highly (at least 10%) branched Phenoxy resin provided with no gelation problems will.

The invention is finally intended to provide a new vesicle-shaped Film made available that has a high-long-chain branched Contains phenoxy resin.

The invention now provides a layerable, high-long-chain-branched, provided non-gelled, non-linear phenoxy resin with any or random structure, the has no regularly recurring units and in which the average distance between the branch points in the is essentially of the same order of magnitude as the average branch length. Such resins are preferred end-blocked and they advantageously comprise the reaction product of

T) at least one dihydric phenol, ·. ■

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2) an epoxy comonomer with two functional epoxy groups,

3) a branching agent comprising an epoxy or

Phenolic compound with a functionality of more than 2, preferably at least 3, the amount used of the branching agent is sufficient to have at least 10, preferably at least 15 to 20 mol% of branching points in the polymer resin, and preferably

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4) a monofunctional phenol or epoxide as an end-blocking compound.

The amount of endblocking compound used is generally that amount which is sufficient to preclude gelation of the phenoxy resin during the polymerization reaction and at the same time the average molecular

5 determine weight.

As used herein, the term "functionality" of a compound means the average number of epoxy or
functional hydroxyl groups of the respective compound. For example, herein under a monofunctional phenol or epoxide
.a compound with a single functional epoxy or
Hydroxy group regardless of the presence of other inert ones
functional groups understood. In fact, the presence of other functional groups which are inert in the copolymerization reaction is also taken into account in the context of the present invention, such as, for example, 2,4,6-trichlorophenol, which compound is suitable as a monofunctional phenol end-blocking compound.

According to a preferred embodiment of the invention that is
branching agents used a trifunctional compound, most preferably triglycidyl-p-aminophenol.

The non-linear, highly branched phenoxy resins of the invention can easily take on a highly viscous nature. The highly branched phenoxy resins are still chemical and thermal extremely stable and they can have excellent properties in terms of stability, increased film speed and show and / or impart the integrity of the chemical structure, when used as a carrier for a vesicular film.

According to a further embodiment of the invention is therefore
provided a vesicular film containing a substrate and a support coated thereon, the coated support containing a dispersed sensitizer such as a diazo compound, which

or which is capable of doing so after exposure to radiation and the subsequent / heat actuated development to create gas bubbles. According to the invention, the stacked Carriers the high-long chain branched phenoxy resins according to the present invention.

For the preparation of the non-linear phenoxy according to the invention Dihydric phenols used in resins can generally be obtained from dihydroxybenzenes and compounds of the formula:

wherein R ₁ , R ^, R- ,, R. are hydrogen, halogen or lower alkyl, η is an integer from 0 to 1, and when η is 1, X is -CH ₂ - -C (CH ₃ J ₂ -, -CH (CH ₃ ) -, -CH-, - (C-CH ₃ ) -,

-0-, -S-, -S- or -S- can be selected.

Mixtures of such dihydric phenols can also be used are and are contemplated within the scope of the present invention.

Examples of suitable dihydric phenols are sulfonyldiphenol, Bisphenol-A, bisphenol-F and resorcinol. These connections represent only examples, without any intention that this should be restricted to the compounds mentioned. Mixtures of such dihydric phenols can also suitably be used.

Sulfonyl diphenol is the most preferred dihydric phenolic reactant and preferably comprises at least 50 mole percent des

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dihydric phenolic reactants. A suitable mixture is, for example a 50/50 molar mixture of sulfonyldiphenol and Resorcinol.

The dihydric phenols are reacted with an epoxy comonomer with two functional epoxy groups. Examples of suitable Diepoxides are the diglycidyl ether of resorcinol, the diglycidyl ether of bisphenol-A, the diglycidyl ether of hydroquinone, the diglycidyl ether of sulfonyldiphenol etc. and Gemisehe of that. The resorcinol diglycidyl ether is the most preferred diepoxide, but mixtures of these can also be used for example 25 mol% of the diglycidyl ether of bisphenol-A contain.

It will be apparent to those skilled in the art that due to the nature of the technical synthesis employed, some of the epoxy reactants May contain synthesis by-products, the functionality of which may differ from that of the main component, what naturally must be taken into account in the calculations for the approaches. "An example of this could be technical resorcinol diglycidyl ether which is usually a bis-like structure with a molecular weight of 388.4 which is difunctional and normally about 7% by weight, as well as a monofunctional one Glycidyl ethers having a molecular weight of 240.3, which is normally used in an amount of about 2 to 4% by weight is present, contains. The analysis of the starting material by chromatography makes it possible to carry out the calculations for the batches adjust accordingly to compensate for the presence of these by-products. This is especially true for the monofunctional Ep'oxy endblocking structure, if used.

In general, any conventionally known divalent Phenols and epoxy compounds suitable for the manufacture of phenoxy resins "are used, provided that that a polymer is obtained which has suitable properties for use as a carrier in a vesicular film.

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The dihydric phenolic and epoxy reactants which are most useful are those which will yield a polymer which has a glass transition temperature above room temperature, preferably in the range used for vesicular film development in commercial equipment, ie in the range of about 100 to 16O ⁰ C, has. Examples of dihydric phenol / diepoxide polymers that give such glass transition temperatures are found in New Linear Polymers by Henry Lee, Donald Stoffy and Chris Neville, published by McGraw Hill,

• 10 1967, pages 45 and 46, listed. Those polymers that by reaction of a dihydric phenol and an epoxy compound. bond are maintained and which the better gas barriers own, Shafts are naturally preferred for vesicular films.

■ · The relative amounts of the dihydric phenol and the diepoxide used for the production of branched phenoxy resins can vary. In general, however, preferably the molar ratio of dihydric phenol to diepoxide comonomers is in the range from about 0.4 to about 2.4, most preferably in the range from about 0.6 to about 1.6. It is also generally preferred that the sum of the equivalents of the phenolic comonomer reactants including any phenolic branching agent and endblocking agent be about the same as the sum of the equivalents of all epoxy comonomer reactants including any epoxy branching agent and endblocking agent. Naturally, this can also vary,

The non-linearity and highly branched structure of the phenoxy resins of the invention results from the incorporation of the branching agent into the polymer. The former includes an epoxy or phenolic compound having a functionality greater than 2, which is preferably in the range of about 2.2 to about 4. Most preferred is a functionality of about 3. The branching agent can be added after the initiation of the polymerization between the dihydric phenol and the epoxy compound

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be so that the branches and interconnections of ": start of Polymerization to be incorporated. But you can also proceed in such a way that the branching agent is added after the introduction or initiation the polymerization clogs. If desired, a mixture of branching agents can also be used.

The amount of epoxy or phenolic branching agent used is generally that amount which is sufficient to at least To give 10 mol% branch points in the polymer resin, thereby ensuring that the phenoxy resin is not a linear resin but a highly branched resin. The most such an amount "is preferred, which is sufficient, that about 15 to 20 mole percent branched sites are obtained in the polymer resin.

The percentage of branch points for the purposes of the present invention is considered to be that amount of the difunctional Reactants of a given chemical type, i.e. either epoxide or phenol, which are represented by branching molecules, i.e. defined by the branching agent in which the polymer chain has been replaced.

Examples of suitable hydroxy branching agents are phloroglucinol, which is a trihydroxy compound and is trifunctional in so far as the polymerization is considered will. Other suitable hydroxy branching agents are, for example, 1,3,8-trihydroxynaphthalene, 2,4,4'-trihydroxydiphenyl, 2,4,4'-trihydroxydiphenyl ether, 2,4,4'-trihydroxydiphenylmethane and diresorcyl sulfide. .

Preferred epoxy branching agents include the multifunctional ones Glycidyl ethers, such as tetrafunctional glycidyl ethers, a. Epoxy novolak resins can also be used, e.g. those having an average functionality of about 3.6, such as one available from Dow Chemical Co. under the designation DEN-438 available epoxy novolak resin.

However, the most preferred epoxy branching agents for the purposes of the present invention are the trifunctional epoxides. A specific example of such trifunctional epoxides which has been found to be best suited for the purposes of the present invention is triglycidyl p-aminophenol, which has been found to be actually tough resins having a branched structure that can be obtained using either a novolak resin or a polyglycidyl ether of a novolak resin is used as a branching agent in the presence of either a monofunctional glycidyl ether or a phenol as an end-blocking agent. Resins which have been produced with an equivalent amount of a trifunctional branching structure, in particular an N-glycidyl branching agent, e.g. triglycidyl-p-aminophenol, have better rheological properties and they are therefore far less susceptible to the development of undesirable microgel particles than Approaches made using novolak materials containing tetra- and pentafunctional components as "part of the inevitable distribution of functionalities in the novolak resin. The replacement of a triglycidyl ether of a" p-aminophenol branching agent with a novolak glycidyl ether branching agent in one approach for an end-blocked resin according to the invention generally results in the formation of undesirable microgel particles.

25 ·

The dihydric phenol, the epoxy compound and the branching agent are preferably used together in the presence of an end blocking compound which is a monofunctional phenol or represents epoxy, reacted with one another. In general, any monofunctional phenol or epoxide can be used with, for practical reasons, most preferred are those that are non-volatile and readily available are available with high purity.

The use of an end blocker in accordance with the present invention is most preferred because it allows the reaction essentially without the risk of gelation

completely expires. Furthermore, the use of the end blocker allows control the molecular weight distribution in a controlled, reproducible and commercially applicable manner. The partial catalyst neutralization and solvent dilution procedures such as those described in U.S. Pat 4 302 524 are simple measures to very rapidly increase the viscosity of a non-end-blocked Balance approach when approaching the gelation point. Such measures not only extend the response time, but also reduce the boiler yield, which are undesirable consequences in both cases. The usage however, an end blocker according to the present invention makes it possible to avoid such undesirable consequences.

It is preferred that the endblocking compound, if is a phenol, has a pka value within about 1 of the dihydric phenol used as the coreactant, to match the speed of reaction. Accordingly, there can be greater control over both gelation and molecular weight distribution will be realized. When using a mixture of dihydric phenols, the endblocking effect depends depends on which pka value of the various dihydric phenols one comes close to. The phenolic endblocking compound only needs a pka value within about 1 of any of the dihydric phenols in the mixture containing the contains dihydric phenolic reactants.

If, for example, sulfonyldiphenol with an epoxy compound and a branching agent in the presence of resorcinol or

'30 bisphenol-A is converted as a second dihydric phenol, then it is preferred to use 4-t-butylphenol as the endblocking agent to use, which indicates the similarity of no pka value to that of resorcinol or bisphenol-A, for example in a 50/50 mixture of sulfonyldiphenol and resorcinol is. In such a case it has been found that the reaction surprisingly occurs at a very rapid rate expires and that still the control of the. Gelling is exceptionally effective.

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7 \ Glycidyl ethers can also be used as end-blocking agents can be used for the purposes of the present invention. When using them, the pka value does not need to be taken into account to become. Accordingly, all epoxy endblocking agents work equally good regardless of what initial reactants are used. Examples of suitable epoxy endblocking: medium are glycidyl ethers, such as n-butyl glycidyl ether, 4-t-butylphenol glycidyl ether, Phenyl glycidyl ether and glycidyl methacrylate.

Of course, mixtures of the two types of endblocking agents, i.e., phenolic and epoxy endblocking agents can be used. Also sharing these End blocking agent is therefore according to the invention in

15 costume drawn.

As in the case of a hydroxy endblocking agent, e.g. 4-t-Buty! Phenol, · is used if a sufficient amount is used - an epoxy end-blocking agent to gel the phenoxy -20 resin excluded. Thus there is the possibility to use the PoIy- { degree of merization of the phenoxy resin and the viscosity of the final solution to control and reproduce without the danger gelation occurs when the appropriate amount of the endblocking agent is used as gelation is precluded will.

The amount of endblocking agent used is generally that amount which is sufficient to exclude gelling of the phenoxy resin during the polymerization reaction and at the same time to determine the average molecular weight. Preferably the amount used is of the endblocking agent at least 5 mol% of the difunctional Reactants of the same chemical nature, i.e. either the epoxy or phenol reactant, which is produced by the monofunctional Endblocking comonomers in the polymer is replaced. The amount of monofunctional endblocking agent used is more preferably in the range of about 5 to 20 mol%, and most preferably in the range of about 5 to 12 mol%.

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The specific selection of the endblocking agent is important because its relative rate of reaction (as compared to the bifunctional and branching functionalities) the speed at which it is incorporated into the polymer chain segments determines and therefore ultimately the molecular weight distribution controlled. While glycidyl ethers all have a similar reactivity towards phenolic components, there is more possibility to manipulate the molecular weight distribution of the polymer, when phenolis the endblocking agents with varying pka value and therefore varying relative reactivity can be used. For example, if one uses a monoglycidyl ether such as phenyl glycidyl ether (in connection with, for example, a polyglycidyl ether branching agent), its chemical reactivity to the phenolic reactants is the same as to all other glycidyl ether reactants, then is used obtain the same specific speed of the competitive reaction and a special molecular weight distribution results. On the other hand, when a monofunctional phenolic endblocking compound such as 4-t-butylphenol or 2,4,6-trichlorophenol, is used, the molecular weight distribution will depend on the pka value of the monofunctional phenol controlled. The latter determines the particular reaction rate compared to the other phenols in the batch. It should also be noted that the use of a glycidyl ether branching agent is also a more uniform one Branching distribution provides, since mono-, di- and triglycidyl ethers are all equally reactive, what for phenolic branching agents, such as novolaks, e.g. against sulfonyldiphenol, is not the case.

This type of manipulation of the distribution, e.g., the use of varying end block levels, in conjunction with varying the identity of the endblocking agent as well as the time of addition during the synthesis gives one advantageous control parameters in the production of the branched resin system according to the present invention, the has not yet been achieved in this area.

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It should also be noted that because the different relative reaction rates of these various endblocking agents allow the molecular weight distribution for a given number average molecular weight To control, a second important advantage of using an endblocking agent according to the invention is obtained becomes, namely the possibility of the rheological properties of the resin solution on special coating techniques align. In particular, phenoxy resin solutions with high viscosity and low solids contents can be produced, which have rheological properties ideally suited for some high precision coating methods · which generally considered better than roll coating techniques, which necessarily require polymers with lower Viscosity such as linear polymers disclosed in U.S. Patent 3,622,333 can be used.

The use of an endblocking agent according to the invention thereby allows the control of the gelation, with further control of the specific molecular weight range and the molecular weight distribution and the reproducibility of these sizes is made possible, so that in effect the resulting branched phenoxy resin can be tailored precisely for the particular application. This will be easy and without knowledge teres obtained because / once the appropriate amount of the endblocking agent has been selected, which on it-. following reaction without the risk of gelation to completion which is in contrast to the process of US Pat. No. 4,330,524.

Although theoretically any phenolic endblocking agent is suitable in practice, it has been found that due to the rapid branching which occurs during the polymerization of approaches with 15 to 20 mol% branching agent takes place, it is preferable to use monophenols, their conjugate bases or bases react quickly enough that they are competitive without relying on an excessively strong initial

concentration must be avoided. In this regard, it has been found that alkylphenols such as para-t-butylphenol or Mesitol, work best when at least some part (preferably up to 50 mol%) of the difunctional phenol a comparable has a pka value like bisphenol-A or resorcinol. For approaches in which only a bifunctional phenol with high acidity, such as sulfonyl diphenol, is used, the alkyl phenols have a different effect from the more acidic monophenols, such as p-chlorophenol, 2,4-dichlorophenol or 2,4,5- and 2,4,6-trichlorophenol. Of course, mixtures of the two can also be used Types of phenolic endblocking agents also used or, as noted above, both epoxy and phenolic endblocking agents can be used simultaneously be used.

In general, the phenol-epoxide interpolymerization is used in the preparation of the non-linear, highly branched one according to the invention Phenoxy resin is best accomplished under alkaline catalysis. Examples in which, for example, aqueous sodium hydroxide solution can be found, for example, in U.S. Patents 3,622-33 and 4,302,524. However, the use of sodium hydroxide as a polymerization catalyst lead to several pronounced disadvantages, since for example 1) the inorganic Salts remaining after neutralization of the catalyst are insoluble in the dry resin film and due to a crystal formation cause optical defects, 2) the existing water can open epoxy rings, whereby the desired Stoichiometry is perturbed and molecular weight growth is limited, and 3) the requirement may be necessary that To dilute the reaction mixture as the reaction proceeds (see e.g. US Pat. No. 4,302,524) in order to prevent gelation, whereby the boiler yield is reduced.

It was found, however, that in contrast to the alkali metal hydroxides and their phenolic salts, tetraalkylammonium bases and salts, are both highly ionic and in organic Media, such as methylcellosolve, are dissociated and on these forms show a superior catalytic activity.

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The catalyst half-life at the typical polymerization is about 4 h at 90 ⁰ C ₇ so that, when carrying out the process at least four half-lives, the residual catalyst content is 6% or less of the original content and no precipitation of the polymer and no washing is needed to to remove either residual salts or low molecular weight polymer fractions which result from a disturbance of the stoichiometry or from a poor catalyst activity. This bypassing the precipitation / washing stage more than compensates for the slightly longer polymerization time, as the cleaning process itself takes much more time, additional vessels, fresh solvent for the redissolution of the polymer, precipitation solvent and the availability of a solvent recovery system to ensure that the to enable / require expensive methyl cellosolves and the precipitation agent.

In the most preferred polymerization process according to the invention, therefore, a volatile catalyst, e.g. tetramethylammonium hydroxide, used, which is at increased tempera ^ ·, doors to trimethylamine and methanol at characteristic speeds, which increase with every increase in temperature, decomposes.

Another preferred catalyst for phenol-epoxy interpolymerization is glycidyltrimethylammonium chloride when combined with an alkali metal hydroxide, e.g. potassium hydroxide, is used. This catalyst is preferred because it is not only an effective catalyst, but can also act as an end-blocking agent.

While the aforementioned alkaline catalysis process is naturally preferred, other polymerization techniques, known in the polymer art can be used.

After the reaction of the dihydric phenol, the epoxy compound

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dung with two epoxy functional groups, the branching agent and preferably the endblocking agent resulting from the phenoxy polymer resin of the present invention is a coatable one or high-long-chain branched, suitable for coating, Non-linear phenoxy resin with a random structure that has no regularly recurring units. The average The distance between the branch points is essentially of the same order of magnitude as the average branch length. The average structure of phenoxypolyning can be shown essentially schematically as follows will:

As always in polymer chemistry, all polymer molecules are natural not the same as there are differences in polymer size and branch lengths. Some Lengths are smaller or larger than others. Not all branches of the phenoxy resin are therefore of the same order of magnitude. like the average distance between the branch points. However, this is the total "average" branch length of the phenoxy resin polymer in the same order of magnitude as the "average" distance between the branches in the polymer. In this sense, the structure given above is an "average" schematic Structure. Furthermore, due to the arbitrary distribution of the branching points and the long-chain branching, there are no any regularly recurring units in the highly branched structure of the phenoxy resin. The invention

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Phenoxy resins are therefore in no way structurally comparable to linear phenoxy resins, but rather have one different high-long-chain-branched structure.

Because of the different non-linear, highly branched structure, the phenoxy polymer resins of the present invention can easily be driven to a degree of polymerization which gives a considerably higher solution viscosity than it generally does can be achieved with corresponding linear resins, which can be achieved by simply reacting the dihydric phenol and the epoxy compound getting produced. These higher viscosity solutions have a desirable elastic behavior and they are for some precision coating techniques work very well, i.e. they can have a viscosity of at least 2500 centipoise. more preferably from 4,000 to 17,000 centipoise, and most preferably from 5,000 to 12,000 centipoise, at a solids content of 30% by weight.

While the non-linear phenoxy resins according to the invention have the advantages of a highly viscous solution, these can also be used. have the same, if not better, properties as linear phenoxy resins. Indeed, non-linear phenoxy resins of low viscosity, for example up to 500 centipoise at 30% by weight solids _{7, can} exhibit a vesicular film which is increased compared to the commercially available linear analog, ie, Xidex-SX film Has film speed.

In general it is assumed that given sufficient Gas barrier properties of the polymer matrix other properties of the polymer, for example those inherent in the polymer structure depend, such as the average molecular weight, the molecular weight distribution and the spatial geometry (linear compared to a branched structure) have little or no influence on the behavior of the film. See e.g. U.S. Patent 3,622,333. According to the invention, however, it has been found that im Contrary to this assumption, the structure and the molecular

Weight distribution of a vesicular matrix resin apparently are very important for the results obtained, since apparently these properties affect the flow characteristics of the matrix during affect the heat treatment stage of film processing. It is believed that without good flow properties the Polymer resistance to internal gas pressure can be high enough that the rate of vesicle growth is significant is reduced and that therefore the achievement of the maximum bubble diameter is largely prevented. See W.J.

Moore, Physical Chemistry, 3rd Edition, Prentice-Hall Inc., p. 729. The more work it takes to expand the molten resin, the less the vesicle will grow for a given initial gas pressure. Since a high resistance to a flow of the matrix which leads to a slower growth of the bubble "also allows a simultaneous loss of gas pressure, the net result of such a situation is poor image density and a population of thermodynamically unstable bubbles which under the thermal stress of particular image stability tests, for example, of 65.6 ⁰ C h 3, coincide. therefore branched polymers in theory, ie, those that are in contrast to linear polymers and have a lighter flow as similar linear polymers with identical molecular weights (cf., for example, LE Nielson, Mechanical Properties of Polymers and Composites, Volume 1, page 104 (1974), FL-. McCrakin and J. Mazur, Macromolecules, Volume 14, No. 5, page 1214 (1981) and J. Roovers and PM Toporowski, Macromolecules, Vol. 14, No. 5, Page 1174 (1981)), give improved behavior in a vesicular film branched end-blocked polymers in a vesicular film give improved performance and, in fact, differ significantly from linear phenoxy resins, as evidenced by the fact that branched matrix resins were found to have an "internal photosensitivities" increase of at least 15% as compared to linear resins (when formulated without nucleation or existing flow additives, so that only the internal or intrinsic properties are measured).

Apart from the use of the non-linear phenoxy resins, the present invention is with the procedures of the Prior art for making a vesicular film in accordance. Thus in every way the details of the prior art can be used, simply instead of the resinous supports of the prior art the non-linear phenoxy resins of the present invention are used.

The vesicle-forming agent used in making the vesicular film is sensitive to radiation, such as light, so that exposure to radiation causes decomposition and formation of gas bubbles, preferably nitrogen. Examples of suitable vesification agents are the following substances:
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p-Diazodiphenylaiuinsulfat, -

p-diazodimethylaniline zinc chloride, p-diazodiethylaniline zinc chloride,
p-diazoethylhydroxyethylaniline.1 / 2 zinc chloride, p-diazomethylhydroxyethylaniline.1 / 2 zinc chloride, p-diazo-2,5-diethoxybenzoylaniline.1 / 2 zinc chloride, p-diazoethylbenzylaniline.1 / 2 zinc chloride, p-diazodimethylaniline borofluoride,

p-Diazo-2,5-dibutoxybenzoylaniline. 1/2 zinc chloride, ' p-Diazo-i-morpholinobenzene. 1/2 zinc chloride, p-Diazo-2,5-dimethoxy-1-p-toluylmercaptobenzene. 1/2 zinc chloride,

p-Diazo-3-ethoxydiethylaniline. 1/2 zinc chloride, p-diazo-2,5-diisopropoxy-1-morpholinobenzene sulfosalicylate,

p-diazo-2,5-diisopropoxy-1-morpholinobenzene triflate, p-diazo-2,5-diethoxy-1-morpholinobenzene sulfosalicylate, p-Diazo-2,5-diethoxy-i-morpholinobenzene triflate, 2,5,4'-triethoxydiphenyl-4-diazonium oxalate, p-Diazodiethy! aniline. 1/2 chloride,

.p-Diazo-2,5-dibutoxy-1-morpholinobenzenechlorid, zinc chloride,

p-Diazo-2,5-dimethoxy-1-morpholinobenzene chloride. Zinc chloride,

p-Diazo-2,5-diethoxy-1-morpholinobenzenechlorid. 1/2 zinc chloride,

2-diazo-1-naphthol-5-sulfonic acid, p-Diazodiethylaniline borofluoride, p-Diazo-2-chlorodiethylaniline. 1/2 zinc chloride-Others suitable photosensitive nitrogen-forming compounds are the quinonediazides (e.g.

and type 20 azide compounds

Also the carbazido (carboxylic acid azide) compounds, which are a Hydroxyl or amino group ortho to the carbazide group according to US Pat. No. 3,143,418 are suitable.

In addition to the progenitor for the vesifying gas, it is common practice to add materials to the coating formulation, which are often referred to as nucleating agents or agents for increasing photosensitivity. These additives must often carefully selected to give high effectiveness in a given matrix resin because they are not can always be used in the same way with a large number of matrix resins. Additives such as the silicones of U.S. Patent 3,779,774 and the fluorocarbons of U.S. Patent 3,779,768

works well in branched phenoxy matrix resins for vesicular Movies, but there are a number of other materials available that perform as well or even better, such as fluorocarbon surfactants available from Ciba-Geigy under the trade names Lodyne S-I03, S-106 and S-107, and silicone wetting agents available from Union Carbide under the trade names L-7001, L-721, L-7000 and Y-7751.

Be in line with the working methods of the prior art.

is the preferred technique for making a vesicle-shaped Film in that first the resin support and the materials disposed therein, such as the vesicle-forming agent, be formulated in a suitable solvent. A range of solvent systems can be used for the present invention Phenoxy resins used are used. The most preferred solvent is methyl cellosolve. Other solvents, which are suitable as diluents for the purposes of the invention are acetone, methyl ethyl ketone, tetrahydrofuran, Dioxane, 2-ethoxyethyl acetate, chlorinated solvents, such as Ethylene dichloride, toluene, and mixtures of such solvents. ·

When using a diazo compound, as is preferred, it is generally in a small amount of a polar solvent such as methanol, aqueous methanol, aceto- '-nitrile or acetone, dissolved and then added dropwise to the stirring phenoxy resin solution to prevent the precipitation of either to minimize the salt or the polymer. The preferred one The amount of the diazo compound is about 4 to 10% by weight of the

30 phenoxy resin used.

When a diazo compound is used as the vesicle forming agent, it is preferred, but it is not necessary that Solvent in which the diazo compound is dissolved is compatible with the solvent selected for the phenoxy resin is to avoid the possibility of the diazo compound or the phenoxy resin precipitating when the two solutions mixed

is minimized. In this area ir. A η knows that a uniform dispersion of the vesicular agent in the Carrier is sought.

When producing a suitable vesicle-shaped film, the resin carrier, the vesicle-forming agent and other ingredients, which can be added contains, coated onto a suitable carrier. As carriers are the different Materials known in the art for this purpose. The most famous materials are polyester films, as indicated by the trademarks Mylar, Estar, Celanar, Lumirror, Hostaphan, etc. :

In addition to the aforementioned ingredients, if desired further additives and treatments, as they are known in this field, are used to achieve beneficial effects will. For example, the hot fluid treatment of US Pat. No. 3,149,971 can be used to create a vesicle Manufacture film according to the present invention if desired.

The invention is illustrated in the examples. In the examples, the photosensitivity was that of the erfindungsgeraektiven Vesicular films produced by phenoxy resins. The general procedure for determination was as follows:

1 . Using a vesicle-free process unit Films (AM Bruning OP-57) were empirically the ·. clearing and development conditions determines the a maximum density of at least 1.8 above Dmin deliver.

2. A control sample of the vesicular film, e.g. Xidex-SX-Films and the test sample were made at identical Conditions processed by contact duplication from a 21-grade silver grade tablet.

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3. The visual transmission density of each level of the silver original and the projection visual density of the control and sample films were then read.

4. Using Cartesian coordinates, the density of each level of the silver original was made on the abscissa and the densities of each respective level of both the control sample and the test sample to the Plotted on the ordinate. Smooth curves were drawn through each set of points.

5. On the control and sample film curves, the points were located with 1.8 density units above Dmin. if Drain was identical on both curves, then the

15 units measured between the two points.

6. When the sample film curve is to the left of the control film curve then the antilog of the number determined in stage 5 was taken and multiplied by 100 to Preserve the photosensitivity of the sample to the control film.

7. If the sample film curve is to the right of the control film curve then the antilog of the number determined in step 5 was taken and the reciprocal of it was multiplied by 100 to get the relative photosensitivity.

8. If the control and test curves in step 4 differ Had Dmin values, then the sample curve point located in step 5 became parallel to the axis of ordinate projected until it was opposite the point located on the control curve at level 5.

9. Using the converted point from step 8, the units were between the control and sample sensitivity points measured, the relative

Photosensitivity of the samples by level 6 or 7 was determined.

In the systems where a Dmax of 1.8 is not obtained above Dmin the sensitivity point was found to be 1.0 D.U. defined above Dmin and levels 5 to 9 were applied.

To be realistic about the behavior of different films of branched Determining end-blocked phenoxy resins has become the most widely used technically at present as a reference standard vesicular film used Xidex SX. As in every film product certain fluctuations from batch to batch must be expected, a dozen were purchased in any order Rolls of film on a developing device (AM Bruning OP-57) were evaluated, and the reference point became average or medium sensitivity value. Thus were with the sole exception of the measurement of the internal or intrinsic sensitivity values, compared to a laboratory-synthesized linear phenoxy resin (in such a way that no nucleating agents and other additives, etc. as present in commercial samples) were all given Photosensitivities in the following examples to the specific average SX photosensitivity normalized.

example 1

A 5-1 resin flask was filled with 501.3 g (3.95 eq.) Of heloxy WC-69 diglycidyl ether of resorcinol (available from -Wilmington Chemical Co.), 121.17 g (1.22 eq .) Triglycidyl-p-aminophenol, 314.8 g (2.52 eq.) 4,4-sulfonyldiphenol, 138.48 g (2.52 eq.) Resorcinol and 28.84 g (0.192 eq.) P-tert .-Butylphenol charged. These materials were dissolved in 24 ml of methyl cellosolve solvent. ^{The solution was heated to 90 °} C. under a nitrogen atmosphere and then catalyzed with 64.8 g of 20% strength by weight methanolic solution of tetramethylammonium hydroxide, diluted with 120 ml of methyl cellosolve. After 20 hours ir. stir

BAD ORIGINAL COPY

at 90 ⁰ C the reaction mixture to 25 ⁰ C was cooled, and any residual alkalinity was dissolved by adding 7.5 g of 36.5% aqueous hydrochloric acid, diluted in 120 ml of methyl cellosolve, neutralized.

It was found that the finally obtained .30 wt .-%

• Solution a Brookfield viscosity of 7457 cp at 21.1 ⁰ C had, which make for precision coating techniques in which much higher viscosities are required, as they are usually necessary when roll coating, suitable.

The suitability of the resin as a matrix for vesicular films was determined on a laboratory scale by producing a top coat and applying it to a film carrier with a Meyer rod or a film substrate is confirmed as follows:

A solution of 2.58 g of 2 _/ 5-diisopropoxy "-4-morpholinobenzene diazonium sulfosalicylate in 11.86 g of methanol was prepared by stirring with a magnetic mixer for 3 to 5 minutes. A second solution has now been prepared by adding, for example, 0.09 g Silicone wetting agent, i.e. Union Carbide L-7001 (as a nucleating and flow additive), was added to 100 g of the 30 wt% solids solution of the matrix resin in methyl cellosolve After the resulting lacquer had passed through a Millipore pre-filter, any resulting air bubbles were allowed to escape and the solution was then applied by hand onto a pre-bond-coated polyester base (usually 127 μm) using a Meyer rod no. 16 stacked so that a dry density of about 5.1 μm was obtained e. The coated base was at ambient temperature for 1 minute allowed to dry before it was transferred to 1 minute in a forced air drying oven of 121.1 ⁰ C.

COPY

badorIginal

This was followed by the general procedure described above the photosensitivity of the vesicle-shaped thus produced Measured film. It was determined to be 129%.

5 Example2

91.76 grams (0.74 epoxy equivalents) of resorcinol diglycidyl ether, 27.00 grams (0.12 epoxy equivalents) of a tetrafunctional glycidyl ether from Shell Oil Co. under the tradename EPON 1031, 52.51 grams (0.417 hydroxy equivalents) of sulfonyl diphenol, 22.02 g (0.400 hydroxy equivalents) of resorcinol and 9.01 g (0.06 hydroxy equivalents) of 4-t-butylphenol were added together with 488 ml of methyl cellosolve as a solvent and 7.2 g of a 20% strength by weight solution of Me ₄ NOH in methanol entered as a catalyst in a reaction vessel. The solution obtained had a solids content of 30% by weight.

The reaction was carried out under nitrogen for 7 hours at 118 ^° C. without gelation of the polymer occurring. The catalyst was neutralized by adding 1 g of 36.5% HCl. The Brookfield viscosity of the final solution was about 1230 cp at room temperature, that is 21.1 ⁰ C determined.

.The photosensitivity of the polymer obtained from vesicle-shaped produced according to the procedure of Example 1 Films were then measured as described above in relation to the widely used technical film Xidex SX. The latter is based on a linear phenoxy resin. The photosensitivity was determined according to the aforementioned general Procedure determined to be 109%.

Example 3

A 5-1 flask was filled with 501.31 grams of resorcinol diglycidyl ether (Heloxy WC-69), 121.17 g triglycidyl-p-aminophenol {Ciba-Geigy 0510), 311.79 g 4,4'-sulfonyldiphenol, 137.16 g resorcinol and 47.7 g of 2,4,6-trichlorophenol, dissolved in 2462 ml of methyl cellosolve,

loaded. The stirred solution was ^{heated to 90 °} C. under a nitrogen atmosphere and catalyzed with 64.8 g of a 20% strength by weight solution of tetramethylammonium hydroxide, dissolved in 120 ml of methyl cellosolve. After 20 h at 90 ^° C., the reaction mixture was cooled to room temperature and the catalyst which remained was neutralized with 7.5 g of 36.5% strength aqueous hydrochloric acid dissolved in 120 ml of methylcellosolve. The Brookfield viscosity of this solution with a solids content of 30% by weight was 5300 cp at 22 ^° C. 10

Example 4

A 5-1 reaction flask was charged with 501.31 g Resorcindiglycidyl- "ether (Heloxy WC-69), 121.17 g · triglycidyl-p-aminophenol (Ciba-Geigy 051O) ₇ 501.04 g of 4,4 '-Sulfonyldiphenol , 73.61 g of resorcinol and 18.74 g of phenyl glycidyl ether were charged. The mixture was then dissolved in 2700 ml of methyl cellosolve. The stirred solution was ^{heated to 110 °} C. under a nitrogen atmosphere and mixed with 64.8 g of a 20% strength by weight methanol -n solution of tetramethylammonium hydroxide, dissolved in 120 ml of methylcellosolve / catalyzed.

After 20 hours at 110 ^° C., the reaction product was cooled to room temperature and neutralized with 7.5 g of 6.5% strength by weight aqueous hydrochloric acid, dissolved in 120 ml of methylcellosolve.

Example -5

A 1-1 reaction flask was filled with 79.3 grams of resorcinol diglycidyl ether (Heloxy WC-69), 42.8 grams of novolak glycidyl ether (DEN-438, available from Dow Chemical Co. ), 105.47 grams of 4,4'-sulfonyldiphenol, and 9 , 4 charged 8 g of 2,4,6-trichlorophenol. These reactants were then dissolved in 534 ml of methyl cellosolve. The reaction solution was heated to 118 to 120 ^° C. under nitrogen, catalyzed with 7.2 g of a 20% strength by weight methanolic solution of tetramethylammonium hydroxide (diluted with 20 ml of methyl cellosolve before addition) and 7.5 at this temperature H

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held long. After cooling to room temperature, the resin solution was neutralized with 1.0 g of 36.5% strength by weight aqueous hydrochloric acid, dissolved in 20 ml of methyl cellosolve. The solution having a solids content of 30 wt .-% hatte'eine Brookfield viscosity of 596 cp at 21.1 ⁰ C at this content of 12 mol% of end-blocker.

Example 6

A 1-1 three-necked flask was filled with 26.99 g (0.151 Ag.) Of epoxidized novolak (DEN-4 38 from Dow Chemical), 124.57 g (0.716 eq.) Of epoxidized bisphenol-A (Dow DER-332 ), 50.06 g (0.400 eq.) Sulfonyldiphenol, 22.02 g (0.400 eq.) Resorcinol and 10.09 g (0.067 eq.) 4-t-butylphenol and the Mixture was dissolved in 56 ml of methyl cellosolve. The polymerization Wurd 3.5 .h at 120 ⁰ C using 7.2 g of a 20% methanol solution of tetramethylammonium hydroxide as a catalyst. After cooling, a solution with a Brookfield viscosity at room temperature of 1208 cp was obtained.

Example 7

A 1-1 reaction flask was charged with 83.55 g resorcinol diglycidyl ether, 20.20 g triglycidyl-p-aminophenol, 2.90 g glycidyl methacrylate, 12.25 g resorcinol, and 83.58 g 4,4'-sulfonyldiphenol. The reactants were then dissolved in 470 ml of methyl cellosolve and the resulting solution was ^{heated to 90 °} C. under nitrogen and catalyzed with 7.2 g of a 20% strength by weight methanolic solution of tetramethylammonium hydroxide (diluted with 10 ml of methyl cellosolve). After 20 hours' at 90 ⁰ C, the reaction mixture was cooled to room temperature and the catalyst was then admixed with 36.5 .-% aqueous hydrochloric acid, dissolved in 10 ml of methyl cellosolve, neutralized. The solution with a solids content of 30 wt .-% had a Brookfield

35 viscosity of 2125 cp at 20.6 ⁰ C.

BATH ORIGINAL

1 copy

• ·

Examples

A 1-1 flask was charged with 83.55 g resorcinol diglycidyl ether, 20.20 g triglycidyl-p-aminophenol, 3.37 g glycidyltrimethylammonium chloride and 111.44 g 4,4'-sulfonyldiphenol dissolved in 518 ml methyl cellosolve. The stirred solution was ^{heated to 114 °} C. under a nitrogen atmosphere and catalyzed with 1.06 g of potassium hydroxide. After 20 h at 114 ° C., the reaction mixture was cooled to room temperature and the remaining catalyst was neutralized with 36.5% strength aqueous hydrochloric acid dissolved in 10 ml of methyl cellosolve. The Brookfield viscosity of this solution with a solids content of 30 wt .-% was 20,500 cp at 20.6 ⁰ C.

. Example9

Following the general procedure of Example 1, several were Phenoxy resins according to the invention prepared, with approximately stoichiometric amounts of a-len phenolic constituents used against all epoxy components. The suitability of the resin as a matrix for vesicle-shaped films was determined on a laboratory scale by preparing a coating varnish and applying it to a film substrate according to the general Procedure of Example 1 tested. The photosensitivity of the vesicular film thus prepared was then determined measured according to the procedure described above. The results obtained are shown in Table I. Even are the relative amounts of the dihydric phenol, diepoxide, branching agent and endblocking agent stated therein.

BAD ORIGINAL COPY

Table I.

co ■ υ m O

Ver B. difunctional difunctional Branching. Triglycidyl-p- Triglycidyl-p- End block Visco React Additives FiIm- Ed. search (At nelles nolles. middle.' (mol%) * aminophenol. aminophenol ki er sity functional recommend SLIDE- game
3) Epoxy phenol (17) (17) middle at tempe- find- Target (mol -%) * (mol%) *. (mol -%) * one rature / lightly- a) Fixed Time speed 4,4'-sulfo-distilled material against nyldiphe- salary SX nol (4 5) from 3 0% + (cp) Λ Resorcinol 4, 4'-sulfo-distilled ** p-t-Bu- 7457 9O ⁰ C / Silicone- 129% _ (At diglyci- nyldiphe- tylphenol 20 h Netzmit game dylether nol (46) (8th) tel 1) (83) + (Union Resorcinol Carbides (46) L-7001) Resorcinol 2,4,6- 5300 9O ⁰ C / - 121% 252 diglyci- Trichloro 20 h lp / mm dylether phenol (83) (10)

Rosorcindiglycidylethor (83)

Resorcinol (45)

4,4'-sulfo-triglycidyl *** - pt-Bu-6013 nyldiphe-p-aminophenol tvlphenol nol (48). (17) " (4)

+ Resorcinol

(48)

120 ⁰ C /
10 h '

Fluorocarbon water: -
fabric + -
Wetting agent (Ciba-Geigy
S-107) '

1 17 '

2 32

lp / mm

moles of the respective epoxy or phenolic components in the phenoxy resin

CJba-Geigy - 0510 *** Ciba-Goigy - 0500 a) with comparable toasting conditions; Range of commercially available SX films from 250-320 lp / mm

Table I continued

Resorcinol digylcidyl ether (83)

Resorcinol diglycidyl ether (78)

Resorcinol diglycidyl ether (80)

Resorcinol diglycidyl ether (80)

Resorcinol diglycidyl ether (83)

4,4'-sulfo-triglycidyl-pnyldipheaminophenol nol (48) (17)

Resorcinol (48)

4,4'-sulfo-distilled nyldiphetes Triglycinol (65) dyl-p-amino-

+ phenol (17) resorcinol

(35)

4,4'-SuIfO-DOW DEN-4 nyldiphe- epoxidized nol (94) novolak (20)

4,4'-SuIfO-DOW DEN-4 nyldiphe- epoxidized nol (94) novolak (20)

4,4'-SuIfo-triglycidyl nyldiphe- p-aminophenol (96) nol (17)

p-t-Bu- 6013 tylphenol (4)

Phenyl 5490 glycidyl ether (5)

p-t-Bu- 1532 tylphenol (6)

120 ⁰ C / silicone 112%

2,4,6-tri-1532 chlorophenol (6)

pt-butylphe-
nol (4)

1175

Netzmit- lp / rrmi tel

(Union Carbide L-7001)

Silicone- 120% mesh mit- lp / mm

9O ⁰ C /
H

(Union Carbide L-7001)

118 ° C / fluorine-7.5 h hydrocarbon wetting agent (S-107)

118 ° C / fluorine-7.5 h hydrocarbon wetting agent (S-103)

12O ⁰ C / fluorohydrocarbon wetting agent (S-107) ■

107% -

104% -

123%

200 lp / mm

CO OJ KJ

* mol% of the respective epoxy or phenolic components in the phenoxy resin

Table I continued

Resorcinol 4,4'-SuIfο- triglycidyl-p-

diglyci- nyldiphe- arainophenol dylether nol (96) (17) (83)

Resorcinol 4,4'-SuIfο- Phlorodiglyci- nyldiphenol glucin (15) dylether (78)
(100)

Resorcinol 4,4'-SuIfO- Triglycidyldiglyci- nyldiphenol ether (15) dylether (90)
(85)

Resorcinol 4,4'-SuIfο- triglycidyl-

diglycinyl dipheisocyanurate. dylether nol (95) (10) (90)

p-t-Bu-1175

tylphe-

nol (4)

2,4,6-tri-226 chlorophenol (7)

4-chloro-495 phenol (100)

2,4,6-135 trichlorophenol (5)

12O ⁰ C / silicone- 126% h wetting agent- lp / mm

tel

(L-7001)

119 ⁰ C / fluorine- 113% h hydrocarbon wetting agent (S-103)

117 ° C / fluorine- 125% 7.5 h carbon

water-

material-

Network-

middle

(S-107)

117 ° C / fluorine- 120% h charcoal-

water-

material-

Network

tel (S-

103)

* mol% of the respective epoxy or phenolic components in the phenoxy resin

1. Example 10

The inner or intrinsic photoencrypts of linear ones and branched carcinogens using identi-

-.5 see film batches that did not contain any added germination aid and ■ subjected to the identical treatment procedures were measured. This must be the decisive factor which governs the size of the photosensitivity, the suitability of the resin structure for application. The attempt was carried out to demonstrate the differences and superiority of the end-blocked branched according to the invention To show resin structures.

Both a branched and a completely linear analog were prepared using the same polymerization conditions in each case. The linear polymers were prepared using stoichiometric equivalent amounts of 4, 4 'dihydroxydiphenyl sulphone and the diglycidyl ether of resorcinol, and by performing the polymerization reaction at "115 to 119 ⁰ C at a concentration of 30% in Methylcellosolvelösung with tetramethylammonium hydroxide as catalyst. The reaction was carried out for periods equal to or longer (ie, 7-10 hours) than the synthesis of the branched resin to obtain a representative sample.

The branched end-blocked resin was obtained by copolymerizing 80 mol% of the diglycidyl ether of resorcinol (RDGE) with the equivalent of 20 mol% of a trifunctional branching unit obtained as an epoxidized novolak (Dow Chemicals DEN-438). The difunctional phenol was 4,4'-dihydroxydiphenyl sulfone (SDP) used in an amount exactly equivalent to the total number of epoxy groups so that gelation except for one. Addition of 15 mol% of 2,4,6-trichlorophenol as an end-blocking agent is unavoidable would have been.

ORIGINAL INSPECTED COPY

The "intrinsic" photosensitivities was · η unt-r use of only 6% by weight of diazo loading in the film and under treatment with a Kodak graduated tablet on a commercially available Processing device (AM Bruning OP-57).

The results obtained are shown in Table II

Table II

Resin SDP Re RDGE mol% Endblok photosensitive type (a) sorc. (b) bifurcation against

(a) Generation (b) medium linear resin

linear

100

end-blocked
branches 100

linear

100

end-blocked
branches 50

0 0

50

100

80 100

20 (c) 0

83 17 (e)

15 (d)
0

8 {f)

100

116 100

115

(a) defined as mol% of the actual amount of difunctionality of the special kind

(b) defined as the inol% of the difunctionality of the same chemical type

25 (c) DEN-4 38 novolak epoxy

(d) .2-, 4, 6-trichlorophenol

(e) Triglycidyl p-p-aminophenol

(f) p-tert-butylphenol

The area of increased intrinsic photo sensitivity that the branched resins of the present invention are useful and significant in commercial practice. He shows up directly indicated by the fact that the resins of the invention the photosensitivity of commercially available vesicle-shaped linear phenoxy films, e.g., Xidex SX, by as much as 29% when used with appropriate nucleation additives are properly worded.

BATH ORIGINAL

Claims (1)

AND APPROVED ^ / REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE »R.WALTER KRAUS DIPLO M CH EM IK ER · D R - 1N G. AN N EKÄTE WEISERT DIPL-ING. CHEMICAL DEPARTMENT IRMGARDSTRASSE 15 · D-BOOO MUNICH 71 · TELEPHONE 089 / 797077-797078 ■ TELEX O5-212156 kpat C TELEGRAM CRAUS PATENT 3882 WK / rra JAMES RIVER GRAPHICS, INC. South Hadley, Massachusetts 01075 / USA Vesicular film element Claims 1. Bubble-shaped film element with a film substrate or carrier and a coating provided for this purpose, which contains a matrix resin and an imaging amount of a photosensitive contains vesicle-forming agent, the latter being designed so that it is after exposure to radiation and subsequent heat-activated development of gas bubbles, characterized in that, that it is used as a matrix resin for the photosensitive vesicle forming Means a layerable, highly branched, non-gelled, with a monofunctional comonomer unblocked, non-linear phenoxy resin with an arbitrary or random structure without regularly recurring ORIGINAL INSPECTED contains units, the average distance between the branches of the resin being substantially from that is of the same order of magnitude as the average branch length. 2. vesicular film element according to claim 1, characterized characterized in that the matrix resin contains or consists of the copolymerization product of the following: 10 1) at least one dihydric phenol, 2) 'an epoxy comonomer with two epoxy functional ones Groups, 3) an epoxy or phenolic branching agent with a functionality greater than 2 and 4) a monofunctional epoxy or phenolic endblocking compound. • 3. The vesicular film element of claim 2 characterized characterized in that the amount of branching agent (3) is such that at least 10 mol% of branch points in the phenoxy resin. ■ ■ · 4. vesicular film element according to claim 2 or 3, characterized in that the branching means (3) has a functionality of about 3. 0 5. bubble-shaped film element according to claim 2 or 3, characterized in that the branching agent is an epoxy compound. 6. 'vesicular film element according to claim 5, characterized characterized in that the branching agent is triglycidyl-p-aminophenol is. 17. vesicular film element according to claim 2, characterized characterized in that the dihydric phenol is a sulfone. 8. vesicular film element according to claim 7, characterized characterized in that the proportion of the bivalent Phenol is at least about 50 molar percent of the sulfonyl diphenol. 9. bubble-shaped film element according to claim 8, characterized characterized in that the dihydric phenol is still resorcinol. 10. vesicular film element according to claim 2, characterized characterized in that the dihydric phenol is resorcinol. 11. vesicular film element according to claim 2, characterized characterized in that the molar ratio of dihydric phenol (1) to diepoxide (2) is in the range of about 0.4 up to 2.4. 12. vesicular film element according to claim 2, characterized in that the end blocking means i 25. (4) is a glycidyl ether. 13. bubble-shaped film element according to claim 2, characterized in that the end blocking means (4) is a phenol whose pka value is within about one Unit of that of at least one divalent phenol (1). 14. bubble-shaped film element according to claim 2, characterized characterized in that the end blocking agent is a mixture of a monofunctional epoxide and a mono- 35 is functional phenol. 15. bubble-shaped film element according to claim 2, characterized marked / that the coating of the element contains a nucleation additive. 16. vesicular film element according to claim 15, characterized 5gekehnzeich.net / that the nucleation additive is a fluorocarbon or silicone surfactant. 17. 'Layerable, high-long-chain-branched, non-gelled, Non-linear phenoxy resin end-blocked with a monofunctional comonomer with any or random structure without regular recurring units, where the average distance between the branch points in the is essentially of the same order of magnitude as the average branch length. 18. Phenoxy resin according to claim 17, characterized in that it is the copolymerization product of the following is:. 20 1) at least one bivalent phenol, 2) an epoxy comonomer with two epoxy functional groups, 3) an epoxy or phenolic branching agent with a functionality greater than 2 and 4) a monofunctional epoxy or phenol endblocking connection. 30th 19. Phenoxy resin according to claim 18, characterized in that that the amount of branching agent (3) is such that at least 10 mol% of branch points in the phenoxy resin. 20. Phenoxy resin according to claim 18 or 19 ·, characterized in that the branching agent (3) has a functionality of about 3. 21. Phenoxy resin according to claim 18 or 19, characterized in that the branching agent is a
Is epoxy compound. 22. Phenoxy resin according to claim 21, characterized in that the branching agent is triglycidyl-paminophenol is. 23. Phenoxy resin according to claim 18, characterized in that g e k e η η, that the dihydric phenol is a sulfon. .24. Phenoxy resin according to Claim 23, characterized in that the proportion of dihydric phenol
is at least about 50 molar percent of the sulfonyl diphenol.
15th 25. Phenoxy resin according to claim 24, characterized in that the dihydric phenol also resorcinol is. 26. Phenoxy resin according to claim 18, characterized in that the dihydric phenol is resorcinol. 27. Phenoxy resin according to claim 18, characterized in that the molar ratio of divalent Phe- nol (1) to diepoxide (2) ranges from about 0.4 to 2.4. 28. Phenoxy resin according to claim 18, characterized in that the end blocking agent (4) is a glycidyl ether is. 30th 29. Phenoxy resin according to claim 18, characterized geke η η
indicates that the endblocking agent (4) is a phenol whose pka value is within about one unit of at least one dihydric phenol (1). 30. Phenoxy resin according to claim 18, characterized in that the end-blocking agent is a mixture is composed of a monofunctional epoxide and a monofunctional phenol. . 31. Coatable, non-gelled, non-linear phenoxy resin with any or random structure, which with a monomeric tri- or tetrafunctional epoxy or phenol compound high-long-chain branched, the branched phenoxy resin has no regularly recurring units and an average distance between the branch points which is of substantially the same order of magnitude as the average branch length. 32. Phenoxy resin according to claim 31, characterized that the monomeric compound has a trifunc- 15 tational connection. 33. Phenoxy resin according to claim 32, characterized in that the compound is triglycidyl-p-aminophenol is.' 34. Bubble-shaped film element having a film substrate and a coating therefor which is a matrix resin and an imaging amount of a photosensitive vesicle forming ' the means, which after exposure to radiation and the following, gas bubbles formed by heat-activated development, characterized in that As a matrix resin for the photosensitive vesicle forming agent, it is a coatable, non-gelled, non-linear one Phenoxy resin with any or random structure that has a high-long chain with a monomeric tri- or tetrafunctional compound has been branched, the branched phenoxy resin contains none has regularly recurring units and an average distance between the branch points of substantially the same order of magnitude as that 35 has average branch length. 35. Film element according to claim 34, characterized in that g e k e η η - indicates that the monomeric branching compound is a trifunctional compound. 36. Film element according to claim 34 or 35, characterized in that that the monomeric branching compound 'is triglycidyl-p-aminophenol. 37. Film-forming, thermoplastic, non-linear, high-long-chain-branched Phenoxyha.rz, thereby g e k e η η - lOzei.chnet that it is the non-gelled reaction product of the following represents: 1) at least one dihydric phenol, 2) an epoxy compound having two epoxy functional ones Groups, 3) an epoxy or phenolic branching agent having a functionality greater than 2, whichever is used The amount of branching agent is sufficient to provide at least 10 mol% of branch points in the polymer resin to surrender, and 4) a monofunctional phenolic or epoxy endblocking. connection. 38. Phenoxy resin according to claim 37, characterized in that the amount of branching agent (3) used is sufficient to branch at least 15 mol% to give generation sites in the polymer resin. 39. Phenoxy resin according to claim 37, characterized in that g e k e η η - ζ-e i c h η e t that the branching agent has a functionality in the range from about 2.2 to about 4. 35 40. Phenoxy resin according to claim 37, characterized in that the branching agent has a functionality of about 3 owns. 41. Phenoxy resin according to claim 37, characterized in that the branching agent is an epoxy compound is. 42. '· Phenoxy resin according to claim 41, characterized / that the branching agent is triglycidyl-paminophenol is. 43. Phenoxy resin according to claim 41, characterized in that g e k e η η draw t- that the branching agent is an epoxy novolak resin with an average functionality of 3.6, is a tetrafunctional glycidyl ether or a trifunctional glycidyl ether. 44. Phenoxy resin according to claim 37, characterized in that g e k e η η - " indicates that the epoxy compound (2) is an aromatic Is diglycidyl ether. 45. phenoxy resin according to claim 4 4, characterized in that g e k e η η, that the epoxy compound (2) 'resorcinol digly- is cidyl ether. 46. phenoxy resin according to claim 37, characterized in that that the dihydric phenol (1) is a di.hy- 25 droxybenzene, a compound of the formula: wherein R, R-, R-, R _{4 represent} hydrogen, halogen or lower al- kyl, η is an integer from 0 to 1 and, when η has the value 1, X is -CH ₃ , -C (CH ₃ J ₃ -, -CH (CH ₃ ) -, -CH- -, 1 OO Il / ^ * - (C-CH-) τ, -Ο-, -S-, -S- or -S- stands, or a mixture da-JL " ö ° 5 of is. 47. Phenoxy resin according to claim 45, characterized in that the dihydric phenol is a sulfone. 48. Phenoxy resin according to claim 47, characterized in that the dihydric phenol sulfonyldiphenol is. 49. Phenoxy resin according to claim 48, characterized in that g e k e η η - shows that the dihydric phenol is still resorcinol. 50. Phenoxy resin according to claim 37, characterized in that the dihydric phenol is resorcinol. 20 - 51. 'Phenoxy resin according to claim 37, characterized in that a mixture of dihydric phenols has been used as component (1). 52. -. Phenoxy resin according to claim 37, characterized in that the molar ratio of dihydric phenol (1) to diepoxide (2) ranges from about 0.4 to 2.4. 53. Phenoxy resin according to claim 37, characterized in that g e k e η η that the amount of endblocking agent present is sufficient to cause gelation of the phenoxy resin to prevent during the reaction. 54. Phenoxy resin according to claim 37 or 53, characterized in that g e that the end block connection (4) is a glycidyl ether. BAD ORfGlNAL - '10 - 55. phenoxy resin according to claim 54, characterized in that the end blocking compound (4) t-butylphenyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether or styrene oxide. 56. Phenoxy resin according to claim 37 or 53, characterized in that the end blocking compound (4) t-butylphenol, p-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol or 2,4,6-trichlorophenol. '· 57. phenoxy resin according to claim 37 or 53, characterized indicates that the endblocking compound is a phenol whose pka value is within about one unit of at least one dihydric phenol, which acts as a 15 tant (1) is used, lies. 58. Phenoxy resin according to claim 53, characterized in that the sulfonyldiphenol and the resorcinol represent components (1) and that the endblocking agent (4) is para-t-butylphenol, the endblocking agent has been used in an amount of from about 5 to about 30 mole percent. 59. phenoxy resin according to claim 37, characterized geke η η - characterized in that the Endblockierungsverbindung is a mixture of an epoxide and phenol. 60. Process for the production of a non-linear, high-long-chain branched, non-gelled phenoxy resin with any or random structure, characterized by that he (1) at least one dihydric phenol, (2) an epoxy compound having two epoxy functional ones Groups, (3) an epoxy or phenolic branching agent with functionality greater than 2 in an amount sufficient that at least 10 mole percent branch sites in the polymer resin are obtained, and (4) a monofunctional phenolic or epoxy endblocking agent in an amount sufficient to prevent gelling of the phenoxy resin, 10 implements. 61. The method according to claim 60, characterized in / that the amount of branching agent (3) used is sufficient to produce at least 15 mol% branching 15 points to yield .. 62. The method according to claim 6O _7, characterized in that the branching agent (3) has a functionality in the range from approximately 2.2 to approximately 4. 63. The method according to claim 60, characterized in that the branching means (3) has a functionality of about 3 owns. 64. The method according to claim 60, characterized in that the end-blocking agent is a glycidyl ether is. 65. The method according to claim 60, characterized in that g e k e η η, that the endblocking agent is a phenol is. ■ 66. The method according to claim 60, characterized in that the reaction is carried out in the presence of 35 performs tetramethylammonium hydroxide. 67. The method according to claim 60, characterized in that g e k e η η - draws that the reaction is carried out in the presence of glycidyltrimethylammonium chloride and carried out by potassium hydroxide. 68. The method according to claim 60, characterized in that g e k e η η drawing net that the amount of dihydric phenol (1) used to the amount of diepoxide (2) used is in the range is from about 0.4 to 2.4. 69. Bubble-shaped imaging element with a sub, strat and a carrier coated thereon which has a dispersed Contains sensitizer which is capable of generating gas bubbles upon exposure to radiation, wherein the carrier is a film-forming, thermoplastic phenoxy polymer which has a gas diffusivity that allows the internal formation of display-defining bubbles of gas which is released by the sensitizer during the heat-actuated Development of the element is released after exposure to radiation, and wherein the phenoxy resin is the The non-linear, ungelled reaction product of claim 37 is. 70. Imaging element according to claim 69, characterized in that the branching means is a. 25 has functionality of about 3. 71. The imaging element of claim 69 or 7O ₇ characterized in that the branching agent is an epoxy compound. 72. The imaging member of claim 69 characterized that the epoxy compound (2) is an aromatic diglycidyl ether. 73. An imaging element according to claim 69, characterized e g indicates that the epoxy compound (2) is resorcinol. 74. The imaging element of claim 69 wherein the sensitizer is a diazo compound is. 75. The imaging element of claim 69, characterized in that the dihydric phenol (1) Is sulfonyldiphenol. 76. The imaging element of claim 75, characterized in that it is identified that the dihydric phenol is still resorcinol. .77. The imaging member of claim 69 characterized in that the endblocking compound is a mixture of an epoxy and phenol. 78. The imaging member of claim 69 characterized in that it is coated onto the substrate ■ Carrier also contains a nucleation additive. 20th 79. An imaging element according to claim 78, characterized in that the nucleating additive is a fluorocarbon or silicone surfactant is. 80. · Mass, characterized in that they a phenoxy resin and a vesicle-forming agent, the phenoxy resin being the non-linear / non-gelled, highly long-chain branched one Reaction product of the following is: 30 (1) at least one dihydric phenol, (2) an epoxy compound having two epoxy groups, (3) an epoxy or phenolic branching agent having a functionality greater than 2, whichever is used The amount of branching agent is sufficient to provide at least 10 mol% of branch points in the polymer resin to surrender, and BAD ORIGINAL COPY - 14 - (4) a monofunctional phenol or epoxide as an end-blocking compound. 81. Composition according to claim 8O _7, characterized in that the mass further contains a nucleating agent. · 82. A composition according to claim 80, characterized in / ₀ -that the mass further comprises a fluorocarbon or silicone surfactant as a nucleating agent. ..